Monoazodyestuffs of the pyrazolone series free from sulfonic acid groups and a process of making same



Patented Aug. 8, 1950 r STATES n w 2,518,078 a t f MONOAZODYESTUFFS or .firnE" PYRAz o; I p w LONE SERIES FREE FROM SULFONIC ACID' ggr ggrs AND A PROCESSLQFY' I r Otto Schmid, Muttenz, and Max'Buchs,

Switzerland, assignors to J.R.;Geigy n, Basel, Switzerland,a,Swiss firm No Drawing. Application January 27, 1947; Se-

.In Switzerland January 31,-.-

rial No. 724,710 1946 r v 1' Among the azo dyestuffs for W001, disazo dyestuffs which are fast "to a. washing, fulling, perspiration and to sea-water'have become important in the trade. Such disazo dyestuffs which Y 12 Claims. (01. 260%162)J{ whereinx means a me 'ber of the group com especially chlorophenyl, naph-' icals', and-Y means a phenese v radicals I being free from sisting or phen thyl and benlz' ylene radical,

often contain an aryl sulfonic acid phenol ester 5 any sulfonic acidgron I l V grouping possess, however, important disadvan- Beside chlorine th'e new dyestufis of themestages, when used forthe wool dyeing. ent invention may 'contain"still further substit- It is a known" factthatfor instance the leveluents usualindyestuffs,-suchfarexample as a1- ling power of such dyestufis on wool is mostly a ky-l groups, alkoxy, aifyloxy, "nitro, acylamino bad one, In practice it vhas been observed that oup d; the like. QEVen, halo f dy -I it is preferable to, give up to some extent the eX- Stuffs fa ling Withiri'the' above Formula I possess cellent fastness properties to washing, fulling, better 'fastnessfprfopertiesto washing, fulling and perspiration and tosea-water in favor of an imto sea-waterfth'an' the Corresponding simple su1-' proved levelling power with the condition that'the foliated pyra j 'Y SWfiSQ Acco d g to .the said'fastness properties are still always good. 15 present invention." the lsaidjproperties can still Thus, dyestufis of good fastness properties to further be improved; when using for the prof washing iulling', perspiration and to sea-Water du ti n'Tof the dyestuffs h pon nts c tain which aretsuperior to the said disazo dyestuffs halogen atoms." Among, halogen-containing with respect to the" levellingpower, but which do compon n sf ay b? l'n s Sta ed above, not attain the excellent fastness properties in he si y i able chlorineand bromine-con the moist stateoi the said disazo dyestufiahave taining components; In -general components con become more important. A further disadvantage .tainingthldrihQwill bepreferred due'to the low of the said disazo. dyestufls consists inllight-iastosts T elhalog'efi c&, be, present ot only in ness propertieswhich do not suffice for modern the coupl n componntbut also in one of'the requirements. radicals ,X "Y and eitl 1fr 'onceor preferably v Now, the present process enables the producseveral n'forinj'oi'substituents. According tion of yellow pyrazolone dyestufis possessing 0 he p ac'of l nkage dy es'tllfiswill be Obtamed better fastness properties in the moist state than which are distinguished by better fastness propth usual guljonat d pyr zolon azo dyestuffs and, erties in the moist state and more particularly improved levelling powerwhen compared with by ajoetter'sea wateriastness of the1W0O1 dye the above mentioned disazo d'yestufis. More paring, while on the othermhand dyestuffs of a very ticularly" it isjpossibleaccording to the present good light-fastness or dyestuffs possessing-"both process to producebetter light-fast dyestuffs posthese pr p rties in an improved degree can be sessi'ng good fastness properties in the moiststate obtained, as Will}- be further illustrated in the and furthermore a good levelling power. pr s n p c fic tio v n ,,We have found that monoa zo dyestuifs consuitable'diazo components enhancing thelighttaining no sulfonic,.acid'groups, but containing a e S 1 h l' Yla O' O y s? halogen atoms and'obtainable from the interduced therefrom-arethose corresponding to 'the action of diazotised aminophenyl-(aryl) or -(arfollowing generalformulae alkyl) -,disulfimides and 5-py f yzolones can be dyed 40 N111 onto wool from anaqueous solution according to a special dyeingmethod used for wool dyestuffs, thus giving well levelled dyeings which, when compared withsimple sulfonated monoazo dyestufis of the pyrazolone series, are distinguished by improved fastness properties to washing, fulling and to sea-water andiwhich possess very good light-fastness properties, the latter properties del r pending upon the constitution of the dyestuffs. W I The new dyestuffs correspondto the following POmPQEGnItSFIRnI-Whiw' :Tepresents' general formula 1 g 5.0 monotil- 01' ti halogenphenyl rad cal, anaphl 'thyl radcalor altetrahydronaphthyl radical, have I 'X'-soe NH--so2--Y'-N=N- 0H00 a favorable, influence onv the fastness properties ;j in the rnoist state or .wool dyeingsproduced 'by 1 t .pyrazolone monoazo dyestuffs. I

- 1 91%: H i rneriaze cpm geeets,usedaqq qi gis thi invention are partly known and partly novel. Their preparation can be effected according to known methods by condensation 'of aromatic or araliphat'ic sulfonio acid halides suitably substituted with aromatic sulfonic acid amides or alkali salts thereof either by melting the components together or in the presence of an inert solvent, like chlorobenzene, .or'rinthepresenoe of! water. The components arerselected such -a manner that the resultant disulfimide will contain a diazotisable amino group or a substituent convertible into such an aniino-group,-=such as a nitro or an acylamino group which, after-having carried out the condensation, will be reduced or saponified'respectively. v

The new dyestuiis are water-soluble, yellow :to orange powders possessing generally a good affinity to animal fibres and dyeing wool in even, greenish-yellow to yellow shades which partly possess remarkably good fastness properties to sea water.

The following examples illustrate the invention Without however limiting the "same. .Parts "by weightbear the same relation'to parts by volume as do grams to cubic centimeters.

.Example 1 36:6 parts of .2-aminopheny1-(T'32fi 3':4"-tetrahydronaphthy'l-F- and -.6')-disulfimide are dissolved in form of the sodium salt -with 5.9 parts of sodium nitrite in "500 parts of water. This solution having a temperature of about 25 C. is caused to .drop at 5 8 G. into "30 "parts or '30 "per cent hydrochloric acid and .the required quantity of ice. 'Ilheeo'lorless diazo suspension is al- The new dyestufl, when dried, is an 'orangeyellow powder -.diss.olvin g in .hot .water and in concentrated sulfuric acid with a bright yellow coloration. When applied :onto -wool from :a neutral to slightly acid bath, the dyestufi shows a very good aflinity and produces even, yellow dyeings of good fastness properties -to washing, fulling and to sea-Water and of very good lightfastness.

The diazo component used in this example can be obtained as follows: 40.4'par ts of o-nitrobenzene sulfamide :are dissolved with 27 parts of 30 per cent sodium hydroxide in 400 parts of water at a temperature of 70 C., 50 parts of a "mixture *of 1i253:- i tetrairydronaphthalene-tiand -6-sulfoni'c acid "chloride, obtained from the technical "mixture "of the sulfonic acids and iiquefied by heating, as well as 31-34 parts of '30 per 'centc'austic soda dye being simultaneously added dropwise to this solution in such a unanher that the same always shows *a phenolphthaleine-alkaline reaction. The reaction product separating out in a crystalline form on cooling is dissolved in water and reduced with iron in an acetic solution-or by means of sodium sulfide according to known methods. The amino compound is a white powder dissolving in hot water on addition of sodium carbonate with development 'of carbon dioxide.

According :to similar methods further diaryl disulfimides can lee-obtained, some of which are enumerated in the following.

A 'dyestufi of similar properties can be obtained, when using in the above example, instead of 'Z-aminop'henyl- (1 :2 :3 :4-tetrahydro- .naphthy1-5'- and -6'.)-disulfimide, 36.8 parts of .Z-aminophenyl-l lemethyl-l' -isopropyl phenyl- 2- and -3')-disulfimide (obtained from a technical cymol monosulfonic acid mixture). It corresponds to the formula on-oo G1 Example 2 36.2 ,parts of Z-aminophenyltnaphthyl 2'f) -disuliimide (in form of the sodium salt) and "6 9 parts oi sodium nitrite ,are dissolved 'in '500 parts of water and the solution warmed up to "30 "C. is caused tofdrop, while stirring, into 30 parts of Bl) per cent hydrochloric acid .and into the required .quantity of ice, the latter mixture being kept at 5-8' 0. After one hour "the yellowish diazosuspension is made neutral to Congo paper by addition of vsodiumlbicarbon'ate"andthen mixed with the solution of '21 parts of 1-(3-chlor.op'heny'l)e3emethyl 5-pyrazolone .in 400 parts .of water admixed with 10 ,parts of 24 .per ,cent 'ammon'ia water. "The mixture is stirred for several hours at lb-12C. and still further seven parts of 24 percent ammonia, water are slowly dropped thereinto. Then the temperature of the mixture is allowed to rise to room temperature and after some hours it .is increased to 40 C. After still .severalhours the dyestuff precipitated in .form of ayellow-orangepowder is filtered off at room temperature. It constitutes, when dried, a yelloworange .powder dissolvin in hot water and in concentrated sulfuric acid with .a bright yellow coloration. "The new dyestuff dyes wool iroma slightly acid bath in even yellow shades of good fas'tness properties to washing, 'fulling and to perspiration and ofa very 'goodlig'ht-fastness.

.Dyestu'fis having similar properties are obtained .by using in the above example, instead of '2-aminophenyl-'(naphthyl 2") disulfimide, 36.2 parts of 2-aminophenyl-'(naphthylql'.) -disulfi- .m'ide.

The diazo components are obtained in the'manner described in Example '1 .from o-nitrobenzen'e suliamide and naphthalene-Z- or -1-su1fon'ic acid chloride inform of white powders easily soluble ,inliot water with sodium carbonate under development of carbondioxide.

Example 32.6 parts of ieaminophenyl-ibenzyl)-disulfi- .mide -(in form of .the sodium salt thereof.) and 6.9 parts of sodium nitrite are dissolved .in .500 parts of water and the resulting solution, after cooling to 20 C., is allowed todrop while stirring at ii-8 C. into 30 parts of 30 per cent hydrochloric acid and into the required quantity of ice. After stirring for "one hour the pure white and-07s:

been added 10 parts of 24 per cent ammonia water. Then the mixture is stirred for 3 hours at 10-12 C. and simultaneously still further parts of 24 per cent ammonia water are added.

The temperature is then slowly raised to 30 C. 1

The'dyest'ufi is and maintained for some hours. precipitated by addition of sodium chloride, filtered by suction and dried. It forms a yellow powder dissolving in hot water, with a yellow coloration and in concentrated sulfuric acid with a greenish-yellow coloration. The dyestuif dyesjjnl wool from a slightly acid bath in yellow, even shades of good sea-water fastness properties.

4-aminophenyl (benzyl) disulfimide can be prepared according to the method indicated in 20 Example 1 by interaction of 4-nitrobenzene sulfamide with nzyl sulfochloride and reduction' of the nitro group with iron in an aqueous acetic acid solution. i

Dyestufis of similar properties will be obtained 25 nitro- 4-chlorobenzene -sulfonic acid amide according to the method disclosed in Example 1 there will be obtained 3-nitro-4-chlorophenylwhen using the same quantity of B-amiimphenyl- (benzyD-disulfimide as diazo component. Simi 4 lar dyestuffs can also be obtainedwith 36 parts, of 3-aminophenyl- (4-ch lorobenzyl) -disulfimid e and with 40.5 parts of B-aminophenyl-(Q-bromo 6 -"""p-chlorophe'nol, to which 10 per cent by weight -of water have'been added. The whole is boiled benzyD-disulfimide as diazo components.

Example 4 38.1. parts of 3-amino-4-chloropheny1 (4' chlorophenyD-disulfimide (as sodium salt) 'and 35 6.9 parts of sodium nitrite are dissolved in 1000 parts of water and the resulting solution having a temperature of 35 C. is allowed to drop while stirringat -10 G. into 30' parts of 30 per cent hydrochloric acid and the necessary quantity of 40 ice. A white crystal paste of the diazo compound, which is completely insoluble in water, thus results; after one hour it is filtered by suc-" tion, sludged with small quantities of ice water and mixed with the solution of 21 parts of 1-(3- tion and in concentrated sulfuric acid with a greenish-yellow coloration. The dyestuff dyes wool from a slightly acid bath in even yellow shades distinguished by good fastness properties to washing, fulling and to sea-water as well as by excellent light-fastness properties.

when using in the above example, instead of 3 amino-4-chlorophenyl (4-chlorophenyl) '-disulfimide, 42.6 parts of 3-;amino-4-chlorophenyl- '(4' bromophenyl)-disulfimide or 37.7 parts of 3-amino 4 chlorophenyl-(4-methoxyphenyl) disulfimide or 40.4 parts of 3-amino-4-ch1orophenyl-(4-acetylaminophenyl) disulfimide as diazo components. The said diazo components can be prepared according to the method described in Example 1. e v

Example 5 50.8 parts of 3-amino-4-(4"-chlorophenoxy)- phenyl (3z4' --di9h1.,orophenyl) -disulfimide (in formof its sodium salt) and 6.9 parts of sodium nitrite are dissolved in 600 parts of water and this solution having a temperature of 40 C. is

"caused to drop, while stirring, at 10 C. into 30 parts of;,30;per cent hydrochloric acid and into the required quantity of ice. The yellowish diazo suspension is stirred for one hour and then mixed with a solution of 21 parts of 1-(3'-chlor ophenyl)-3-methyl-5-pyrazolone in 400 parts of "water previously treated with 13.5 parts of 30 per cent caustic soda lye and parts of sodium carbonate.

The mixture is first stirred at 10 C. for 3 hours, then at room temperature for 10 hours and finally at; 35-40 C. for still further 3 hours.

The so-formed dyestuff is filtered by suction at room temperature and dried. It constitutes an orange-yellow powder dissolving in hot water as well as in concentrated sulfuric acid with a yellow coloration.

be prepared as follows: By condensation of -3:4.

dichlorobenzene sulfonic acidchloride with 3- (3:4-dichlorophe nyl)-disulfimide which is dissolved in the threefold theoretical quantity of under reflux, while dropping thereinto within 1 hour the theoretical quantity of' per cent caustic soda lye. Then the mixture is stirred under reflux for still 10 hours, whereupon the chlorophenol present in excess is removed by steam distillation and the yellow solutioriis reduced'with iron and acetic acid. In this way 3-amino 4 (4"-ch1orophenoxy) -phenyl-(3':4'- dichlorophenyl)-disulfimide is obtained in form of a white powder dissolving in hot water after addition of sodium carbonate with development of carbon dioxide.

Dyestuffs of similar properties are obtained, when substituting the 3-amino-4-(4"-chlorophenoxy) -pheny1- (3 :4'-dichlorophenyl) disulfimide. in the above example by 47.3 parts of 3-amino 4 phenoxyphenyl (3':4' dichloro- 4 phenyl) -disulfimide or by 45.3 parts of 3"-aminootherwise working in ananalogous manner. The latter diazo components can also be made according'to the above described method.

The production of further diazo components can be carried out in an analogous manner to the method disclosed in details in Example 1.

Dyestufis of similar properties can beobtamd, With respect thereto it may be noted that for the manufacture of a diaryl disulfimide of the general formula A'SO2NHSO2B two different ways are possible which can be represented by the following 2 formulae and ASO2NHNa.-+C1SO2B. It can be observed that often both these ways will not give the same yields so that it may be advantageous to determine by a previous experiment the more favorable method for the intended purpose.

Some further dyestuffs illustrating the objects of the present invention will be shown in is the following table. All these dyestuffs can be 7 made according to the methods disclosed in the above examples, while using the diazo compo nents and the coupling components shown in said'table.

8 wherein X-and Y have the above defined meanings.

2. Process for the manufacture of a yellow mono'azo dyestuff of the pyrazolone series, tree Formulae of representative dyestuffs of the pre- 35 ceding table are as follows: 1)"

()1 s Or-NH S o r N=N-o H=C Q Q \N CHa-C N (7) 01 Q1 N-nN on-oo s. l 7 r N Q-SOz-NH-SOz-OCI :N Cl 8H: 45 (10) Cl What we claim is: 1. Process for the manufacture of a yellow monoazo dyestuff of the pyrazolone series, free from sulfonic acid groups, hydroxy groups and carboxylic acid groups, and corresponding to the general formula wherein X stands for a member selected from the group consisting of chlorophenyl, naphthyl and benzyl radicals and Y stands for a phenylene radical, which comprises coupling a diazotised amine of the general formula XSO2NH--SO2YNH2 with a 5-pyrazo1one of the formula Cl OHa-CO from sulfonic-acid groups, hydroxy groups and carboxylic acid groups, and'corresponding to the general formula 01 .XASOPNBF-SOT-OCI l O H-oo wherein X stands for a member selected from the group consisting of chlorophenyl, naphthyl and benzyl radicals, which comprises coupling a diazotised amine of the general formula NHa with a 5-pyrazo1one of the formula CH3 C1 CHFCO wherein X has the above defined meaning.

3. Process for the manufacture of a yellow monoazo dyestuff of the pyrazolone series, free from sulfonic acid groups, hydroxy group and carboxylic acid groups, and corresponding to the general formula om- N wherein'X stands for a member'selected from the group'consisting of chlorophenyl, naphthyl and benzyl radicals, which comprises coupling a diazotised amine of the general formula x-sm-N'm-so; NH:

with a .5-pyrazolone of the formula I one-o OH :N wherein X has the above defined meaning.

4. Process for th manufacture of a yellow monoazo dyestufi free from sulfonic acid groups of the formula which comprises coupling diazotised 3-amino-4- chlorophenyl- (4-ch1orophenyl) disulfimide with 1- (3-chlorophenyl) -3-methy1-5-pyrazolone.

5. Process for the manufacture of a yellow monoazo dyestuff free from sulfonic acid groups of the formula CH2 Cl SOz-NH-SO: N=NCH-CO I H2 I N- which comprises coupling diazotised Z-aminophenyl (tetrahydronaphthyl) disulfimide with 1- 3-ch1or0phenyl) -3-methyl-5-pyrazolone.

6. The yellow monoazo dyestuff of the pyrazolone series, free from sulfonic acid groups, hydroxy groups and carboxylic acid groups, of the general formula CH ==N wherein X stands for a member selected from the group consisting of chlorophenyl, naphthyl and benzyl radicals andY stands for a phenylene radical.

'7. The yellow monoazo dyestuff of the pyrazolone series, free from sulfonic acid groups, hydroxy groups and carboxylic acid groups, of the general formula x-soi-Nn-soQm wherein X stands for a member selected from the group consisting of chlorophenyl, naphthyl and -gloenzyl radicals.

8. The yellow monoazo dyestuff of the pyrazp qne s e free from 14E991? e9 9 g P P 10 droxy groups and carboxylic acid groups, of the general formula wherein X stands for a member selected from the group consisting of chlorophenyl, naphthyl and benzyl radicals.

9. The yellow monoazo dyestuff of the formula N=NCH-C9\ G1 CIOSOg-NH-SOpO-Cl l )O I 0113- =N 10. The yellow monoazo dyestuff of the formula CH2 I N=NCH-CQ l -C oHa-o==N 11. Process for the manufacture of a yellow monoazo dyestufi, free from sulfonic acid groups, of the formula y QSOz-NH-SOr or 1 JJH:

O'I'IO SCHMID. MAX BUCHS.

REFERENCES CITED The following references are of record in the file of this patent: v

UNITED STATES PATENTS Number Name Date 1,876,884 Eiohwede et a1 Sept. 13, 1932 2,199,043 Conzetti Apr. 30, 1940 2,295,050 Reynolds Sept. 8, 1942 FOREIGN PATENTS Number Country Date 5 2 France m;- Ju i 9 8 

6. THE YELLOW MONOAZO DYESTUFFS OF THE PYRAZOLONE SERIES, FREE FROM SULFONIC ACID GROUPS, HYDROXY GROUPS AND CARBOXYLIC ACID GROUPS, OF THE GENERAL FORMULA 